JPH02184646A - Phenol separation method - Google Patents
Phenol separation methodInfo
- Publication number
- JPH02184646A JPH02184646A JP1300955A JP30095589A JPH02184646A JP H02184646 A JPH02184646 A JP H02184646A JP 1300955 A JP1300955 A JP 1300955A JP 30095589 A JP30095589 A JP 30095589A JP H02184646 A JPH02184646 A JP H02184646A
- Authority
- JP
- Japan
- Prior art keywords
- phenol
- membrane
- xylene
- alkyl
- alkylphenol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims description 23
- 238000000926 separation method Methods 0.000 title claims description 6
- 239000012528 membrane Substances 0.000 claims description 37
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 19
- 239000008096 xylene Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 18
- -1 polydimethylsiloxane Polymers 0.000 claims description 16
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 9
- 238000006473 carboxylation reaction Methods 0.000 claims description 8
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 8
- 150000002989 phenols Chemical class 0.000 claims description 8
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 8
- 230000021523 carboxylation Effects 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 230000008961 swelling Effects 0.000 claims description 4
- 239000011159 matrix material Substances 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-M phenolate Chemical compound [O-]C1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-M 0.000 claims description 2
- 229940031826 phenolate Drugs 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- 230000003381 solubilizing effect Effects 0.000 claims description 2
- ZGJADVGJIVEEGF-UHFFFAOYSA-M potassium;phenoxide Chemical compound [K+].[O-]C1=CC=CC=C1 ZGJADVGJIVEEGF-UHFFFAOYSA-M 0.000 claims 1
- NESLWCLHZZISNB-UHFFFAOYSA-M sodium phenolate Chemical compound [Na+].[O-]C1=CC=CC=C1 NESLWCLHZZISNB-UHFFFAOYSA-M 0.000 claims 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 11
- 239000011734 sodium Substances 0.000 description 11
- 229910052708 sodium Inorganic materials 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000012466 permeate Substances 0.000 description 10
- 229960001860 salicylate Drugs 0.000 description 7
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 239000003518 caustics Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000005804 alkylation reaction Methods 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000012465 retentate Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000011144 upstream manufacturing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- ABBQHOQBGMUPJH-UHFFFAOYSA-M Sodium salicylate Chemical compound [Na+].OC1=CC=CC=C1C([O-])=O ABBQHOQBGMUPJH-UHFFFAOYSA-M 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229920005560 fluorosilicone rubber Polymers 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229960004025 sodium salicylate Drugs 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/70—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/70—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment
- C07C37/82—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment by solid-liquid treatment; by chemisorption
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/47—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C65/00—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C65/01—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing hydroxy or O-metal groups
- C07C65/03—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing hydroxy or O-metal groups monocyclic and having all hydroxy or O-metal groups bound to the ring
- C07C65/05—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing hydroxy or O-metal groups monocyclic and having all hydroxy or O-metal groups bound to the ring o-Hydroxy carboxylic acids
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
り業上皇Ｕ分見
本発明は、フェノールのカルボキシル化によって得られ
た混合物からフェノールを分離する方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for separating phenol from a mixture obtained by carboxylation of phenol.
の
アルキル置換フェノールがアルキルサリチレートに変換
される場合、収率は一般に約７５％である０反応器への
再循環が適用される場合、収率は約８２％に増大される
。アルキル置換フェノールとアルキルサリチレートは分
離が困難であるので、フェノールは実際にはこれまで除
去されなかった。When alkyl-substituted phenols are converted to alkyl salicylates, the yield is generally about 75%; when recycle to the zero reactor is applied, the yield is increased to about 82%. Because alkyl-substituted phenols and alkyl salicylates are difficult to separate, phenol has not been practically removed to date.
かかるアルキルサリチル酸の過剰塩基化（ｏｖｅｒｂａ
ｓｅｄ）カルシウム塩の製造においては、フェノールは
何ら害を与えない、しかしながら、アルキル置換フェノ
ールが分離されそしてアルキルサリチレートの製造の出
発物質として再び用いられ得ることが好ましいであろう
、全体的な反応において、アルキルフェノールに基づい
て計算してはるかに高い収率のアルキルサリチレートが
得られ得よう。Overbasing of such alkylsalicylic acids
sed) In the production of calcium salts, phenols do not pose any harm; however, it would be preferable that the alkyl-substituted phenols can be separated and used again as starting material for the production of alkyl salicylates, since the overall In the reaction, much higher yields of alkyl salicylate calculated on the alkyl phenol could be obtained.
晋 ゛ ・の
フェノールを選択的に吸収するメンブランを用いてフェ
ノールがサリチレートから分離され得る、ということを
本発明者は今般見出した。The inventors have now discovered that phenol can be separated from salicylate using a membrane that selectively absorbs phenol.
本発明は、フェノールのカルボキシル化によって得られ
かつフェノール、フェノラート及びカルボキシル化生成
物を含有する混合物からフェノールを分離する方法にお
いて、該フェノールをメンブランの一方の壁に選択的に
吸収させ、該メンブランのマトリックスに該フェノール
を可溶化させ、該フェノールを該メンブランに拡散させ
そして該フェノールを他方の壁から肌着させることによ
り該分離を行う、ことを特徴とする上記方法に関する。The present invention provides a method for separating phenol from a mixture obtained by carboxylation of phenol and containing phenol, phenolate and carboxylation product, in which the phenol is selectively adsorbed onto one wall of a membrane. The above method is characterized in that the separation is carried out by solubilizing the phenol in a matrix, diffusing the phenol into the membrane and skinning the phenol from the other wall.
アルキルサリチレートは、次の逐次反応により製造され
得る：
（１）アルキル化
ここで、Ｒ′はＲより炭素原子が２個少ないアルキル基
である。Alkyl salicylates may be prepared by the following sequential reactions: (1) Alkylation where R' is an alkyl group having two fewer carbon atoms than R.
（２）フェノラート化
（３）カルボキシル化
（４）更に、次の平衡反応が起こる：
Ｒは、好ましくは２〜２０個の炭素原子−層好ましくは
１０〜１８個の炭素原子を有するアルキル基である。(2) Phenolation (3) Carboxylation (4) Furthermore, the following equilibrium reactions take place: R is an alkyl group preferably having 2 to 20 carbon atoms - preferably 10 to 18 carbon atoms. be.
アルキル化反応中製造されるアルキル化フェノールは、
好ましくはアルキル基の混合物を含有しそして反応状況
に依り２０％までのジアルキル化化合物を含有しさえし
得る。The alkylated phenol produced during the alkylation reaction is
Preferably it contains a mixture of alkyl groups and may even contain up to 20% dialkylated compound depending on the reaction situation.
上記（４）の平衡反応の混合物がメンブランにより精製
される場合、アルキルＷ換フェノールが浸透現象により
取り去られるので平衡反応は右側に移る。When the mixture of the equilibrium reaction in (4) above is purified by a membrane, the equilibrium reaction shifts to the right side because the alkyl W-converted phenol is removed by the osmosis phenomenon.
過剰塩基化カルシウムアルキルサリチレートを製造する
ためには、次の反応が行われ得る：（５）酸性化
（６）Ｃａでの中和
（７） Ｃａ （ＯＨ）ｉ＋ ＣＯｘでの過剰塩基化。To produce overbased calcium alkyl salicylates, the following reactions may be performed: (5) acidification (6) neutralization with Ca (7) overbasing with Ca(OH)i+ COx .
上記の（２）及び（３）におけるフェノラート化及びカ
ルボキシル化は、好ましくは溶剤例えば芳香族炭化水素
の存在下で行われる。芳香族炭化水素の例は、ベンゼン
、トルエン、０−ｌｍ−又はＰ−キシレンあるいはそれ
らの混合物である。フェノラート化反応においてＮａＯ
Ｈを用いる代わりに、ＫＯＨも用いられ得る。溶剤特に
キシレンは、使用メンブランに対して膨潤剤として働き
得る。The phenolation and carboxylation in (2) and (3) above are preferably carried out in the presence of a solvent such as an aromatic hydrocarbon. Examples of aromatic hydrocarbons are benzene, toluene, O-lm- or P-xylene or mixtures thereof. NaO in the phenolation reaction
Instead of using H, KOH can also be used. Solvents, especially xylene, can act as swelling agents for the membranes used.
メンブランは、「キルクーオスマー（Ｋｉｒｋ−Ｏｔｈ
ｍｅｒＬ ”化学技術の百科辞典（Ｅｎｃｙｃｌｏｐｅ
ｄｉａ ｏｆＣｈｅ＋１ｉｃａｌ Ｔｅｃｈｎｏｌｏｇ
ｙ）’＋第３版、パート上ｌ」の第９２頁等に非常に詳
しく記載されている。The membrane is called “Kirk-Othmar”.
merL “Encyclopedia of chemical technology”
dia of Che+1ical Technology
y)' + 3rd edition, Part 1, page 92, etc., is described in great detail.
特定物（ｓｐｅｃｉｅｓ）がメンブランを通じて輸送さ
れ得るところの非常に重要でかつ基本的な手段は、透過
物分子（アルキル化フェノール）をメンブラン中にその
上流表面にて溶解させ、そしてその後その濃度勾配に沿
ってメンブランの下流面に分子を拡散させることを含む
、その際、アルキル化フェノールはその隣接の流体相中
に溶解される。A very important and fundamental means by which species can be transported through a membrane is to dissolve permeate molecules (alkylated phenols) into the membrane at its upstream surface and then add it to the concentration gradient. the alkylated phenol is dissolved into the adjacent fluid phase.
溶剤をメンブランに拡散させるための推進力は、当該系
にかけられる圧力である。フェノールの輸送のための推
進力は、濃度勾配である。実際、推進力をなすのは、メ
ンブランの両側における圧力差及び濃度差である。The driving force for the diffusion of solvent into the membrane is the pressure applied to the system. The driving force for phenol transport is the concentration gradient. In fact, it is the pressure and concentration differences on both sides of the membrane that provide the driving force.
本発明による方法において用いられる好ましいメンブラ
ンは、緻密な架橋エラストマーメンブラン例えばポリイ
ソプレン、ポリブタジェン、ポリジメチルシロキサン及
びフルオロシリコンのゴムである。緻密メンブランは、
一般に特定物を選択的に輸送する能力を有する。しかし
ながら、緻密メンブランは、低輸送速度を有し得る。許
容可能な輸送速度を達成するためには、メンブランを薄
く好ましくは非常に薄くすることが必要である。Preferred membranes used in the method according to the invention are dense crosslinked elastomeric membranes such as polyisoprene, polybutadiene, polydimethylsiloxane and fluorosilicone rubbers. The dense membrane is
It generally has the ability to selectively transport specific substances. However, dense membranes can have low transport rates. In order to achieve acceptable transport rates, it is necessary for the membrane to be thin, preferably very thin.
それ故、緻密メンブランを多孔支持体上に施すことが有
利であり得る。メンブランの上流面にかけられる圧力は
、一般に分離工程中１−１００バール（１００〜１０，
０００ ｋＰａ）の範囲にある０本発明による方法に用
いられる湿度は、０゛Ｃないし１２０℃好ましくは５０
℃ないし９０℃の範囲にある。It may therefore be advantageous to apply a dense membrane on a porous support. The pressure applied to the upstream face of the membrane is generally between 1 and 100 bar during the separation process.
The humidity used in the method according to the invention is in the range 0°C to 120°C, preferably 50°C.
It is in the range of ℃ to 90℃.
メンブランとして用いるのに特に重要なものは、オルガ
ノポリシロキサン例えばポリジメチルシロキサンである
。Of particular interest for use as membranes are organopolysiloxanes such as polydimethylsiloxane.
アルキルフェノールは、メンブランを通過する全流出量
の一部にすぎない、透過物は、アルキルフェノールの苛
性反応の際に反応器又は蒸留カラムに再循環され得る。The alkylphenol is only part of the total effluent passing through the membrane; the permeate can be recycled to the reactor or distillation column during the caustic reaction of the alkylphenol.
メンブランはアルキルフェノールに対して高選択性であ
り、何故ならナトリウムアルキルサリチレートは透過物
中に認められないからである。The membrane is highly selective for alkylphenols since no sodium alkylsalicylates are found in the permeate.
カルボキシル化アルキルフェノール生成物（ナトリウム
アルキルサリチレート）中のアルキルフェノールの量は
、かなり減じられ得る。アルキルフェノールは、カルボ
キシル化反応に再び用いられ得る。キシレン及びアルキ
ルフェノールからなる透過物のキシレンは、留去されそ
してフェノラート化反応にあるいはメンブラン分離過程
用の膨潤剤として用いられ得る。The amount of alkylphenol in the carboxylated alkylphenol product (sodium alkyl salicylate) can be significantly reduced. The alkylphenol can be used again in the carboxylation reaction. The permeate xylene, consisting of xylene and alkylphenols, can be distilled off and used in the phenolation reaction or as a swelling agent for membrane separation processes.
工嵐■
例Ｉ
ＣＩ４〜Ｃ１，アルキル基を含有する苛性アルキルフェ
ノールをキシレンと混合し、そしてその混合物を加熱し
てキシレンと水の共沸混合物を留去させた。該共沸混合
物を集め、そして水とキシレンに分離した。このキシレ
ンを、該苛性アルキルフェノールとキシレンとの混合物
に再循環させた。EXAMPLE I CI4-C1, a caustic alkylphenol containing an alkyl group, was mixed with xylene and the mixture was heated to distill off the azeotrope of xylene and water. The azeotrope was collected and separated into water and xylene. The xylene was recycled to the caustic alkylphenol and xylene mixture.
該アルキルフェノールを反応器中に導き、そしてキシレ
ン溶液中で二酸化炭素と反応させた。キシレンと一緒に
アルキルフェノール及びナトリウムアルキルサリチレー
トを含んでなる得られた反応生成物を、実験に用いた。The alkylphenol was introduced into a reactor and reacted with carbon dioxide in xylene solution. The resulting reaction product comprising alkylphenol and sodium alkylsalicylate along with xylene was used in the experiments.
キシレン中に熔解しているアルキルフェノール及びナト
リウムアルキルサリチレートの溶液を、１０、２ ｃ＋
ｌｌの面積を有するポリジメチルシロキサンメンブラン
の高圧側に６０℃の湿度、５〜４０バール（５００〜４
０００ ｋＰａ）の透過圧にてポンプ輸送した。該圧力
は空気加圧ベロー管を用いて維持し、残留物溶液はロー
タリーポンプを用いて再循環させた。透過物溶液は、メ
ンブランの下流側にて再循環系の外で集めた。A solution of alkyl phenol and sodium alkyl salicylate dissolved in xylene was prepared at 10,2 c+
The high-pressure side of a polydimethylsiloxane membrane with an area of
000 kPa). The pressure was maintained using an air pressurized bellows tube and the retentate solution was recirculated using a rotary pump. The permeate solution was collected outside the recirculation system downstream of the membrane.
７５．５重量％のキシレン及び合計で２４．５重量％の
アルキルフェノール及びナトリウムアルキルサリチレー
ト（アルキルフェノール／ナトリウムサリチレートの重
量比は０．２１）からなる供給物は、６時間後６６．４
重量％のキシレン及び合計で３３．６重量％のアルキル
フェノール及びナトリウムアルキルサリチレート（アル
キルフェノール／ナトリウムアルキルサリチレートの重
量比は０．１８）からなる残留物をもたらした。透過物
は、９４．５重量％のキシレン及び５．５重量％のアル
キルフェノールを含有していた。透過物中には、ナトリ
ウムアルキルサリチレートは認められなかった。A feed consisting of 75.5% by weight of xylene and a total of 24.5% by weight of alkylphenol and sodium alkyl salicylate (the weight ratio of alkylphenol/sodium salicylate is 0.21) was 66.4% by weight after 6 hours.
This resulted in a residue consisting of % xylene by weight and a total of 33.6% by weight alkylphenol and sodium alkylsalicylate (alkylphenol/sodium alkylsalicylate weight ratio 0.18). The permeate contained 94.5% xylene and 5.5% alkylphenol by weight. No sodium alkyl salicylate was observed in the permeate.
メンブランにかけられた圧力は、最初の３時間は５バー
ル、３時間から４時間までは２０バールそして最後の２
時間（即ち、４時間から６時間まで）は４０バールであ
った。１時間ごとに、流出量が測定された。ポリジメチ
ルシロキサンメンブランを通過した全流出量は、５バー
ル、２０バール及び４０バールの圧力にてそれぞれ４０
０ ｆｆｉ／ポ０日、１ＩＱＱｆｆｉ／ポ０日及び１４
００ｆｆｉ／ポ。The pressure applied to the membrane was 5 bar for the first 3 hours, 20 bar for 3 to 4 hours and 20 bar for the last 2 hours.
The time (ie from 4 to 6 hours) was 40 bar. Efflux was measured every hour. The total flow rate through the polydimethylsiloxane membrane was 40 at pressures of 5 bar, 20 bar and 40 bar, respectively.
0 ffi/po 0 days, 1IQQffi/po 0 days and 14
00ffi/po.
日であった。It was day.
ポリジメチルシロキサンメンブランを通過したアルキル
フェノールの流出量は、実験の始まりにおいて１４０
ｆｆｉ／ｒｒｆ、日であったが５バールの圧力において
６０１１／ｒｒｆ、日に減じられた。圧力を２０バール
及び４０バールに増大すると、それぞれ７０ ｆ／ｒｒ
ｆ、 日及び８０ｆｆｉ／ｎｆ９日のアルキルフェノー
ル
は、アルキルフェノールの流出量に関して適度の増大を
もたらすがキシレン流出量に関してはがなりの増大をも
たらす。透過物中にナトリウムアルキルサリチレートが
検出され得なかったので、アルキルフェノールの高選択
性分離が達成された。The flow rate of alkylphenol through the polydimethylsiloxane membrane was 140% at the beginning of the experiment.
ffi/rrf, day, but was reduced to 6011/rrf, day at a pressure of 5 bar. Increasing the pressure to 20 bar and 40 bar respectively gives 70 f/rr
Alkylphenol at f, day and 80ffi/nf9 day results in a moderate increase in alkylphenol flux but a large increase in xylene flux. Highly selective separation of alkylphenols was achieved as no sodium alkylsalicylates could be detected in the permeate.
例■
６９、４重量％のキシレン及び合計で３０．６重量％の
アルキルフェノール及びナトリウムアルキルサリチレー
トからなる供給物を、１０．２ｃｄの面積を有するポリ
ジメチルシロキサンメンブランの高圧側に６０℃の湿度
、２ ０バール（２ ０ ０ ０ ｋＰａ）の圧力にて
ポンプ輸送した．該圧力は空気加圧ベロー管を用いて維
持し、残留物溶液はロータリーポンプを用いて再循環さ
せた．透過物溶液を、メンブランの下流側にて再循環系
の外で集めた．実験は約４日続けた．実験中、新鮮なキ
シレンを時々供給物に供給することにより供給物中のキ
シレン濃度を供給物の６３〜８７重量％に維持した（こ
の処置を取った理由は、キシレンは高速度（アルキルフ
ェノールの速度と比べて）にてメンブランを拡散するか
らである）。Example ■ 69. A feed consisting of 4% by weight xylene and a total of 30.6% by weight alkylphenol and sodium alkyl salicylate was placed on the high pressure side of a polydimethylsiloxane membrane having an area of 10.2 cd at 60°C humidity. , pumped at a pressure of 20 bar (2000 kPa). The pressure was maintained using an air pressurized bellows tube and the retentate solution was recirculated using a rotary pump. The permeate solution was collected outside the recirculation system downstream of the membrane. The experiment lasted about 4 days. During the experiment, the xylene concentration in the feed was maintained between 63 and 87% by weight of the feed by occasionally feeding fresh xylene into the feed (the reason for this was that (compared to ).
結果を次表に示す。The results are shown in the table below.
透過物はいずれも、ナトリウムアルキルサリチル酸を含
有していなかった。従って、ポリジメチルシロキサンメ
ンブランは、アルキルフェノールに対して高選択性であ
る。約４日後、当初の供給物混合物中のアルキルフェノ
ールはかなり減じられた。None of the permeate contained sodium alkylsalicylic acid. Therefore, polydimethylsiloxane membranes are highly selective for alkylphenols. After about 4 days, the alkylphenols in the original feed mixture were significantly reduced.
代理人の氏名 川原１）−穂Agent's name: Kawahara 1) - Ho
Claims (12)
フェノール、フェノラート及びカルボキシル化生成物を
含有する混合物からフェノールを分離する方法において
、該フェノールをメンブランの一方の壁に選択的に吸収
させ、該メンブランのマトリックスに該フェノールを可
溶化させ、該フェノールを該メンブランに拡散させそし
て該フェノールを他方の壁から脱着させることにより該
分離を行う、ことを特徴とする上記方法。(1) A method for separating phenol from a mixture obtained by carboxylation of phenol and containing phenol, phenolate and carboxylation product, in which the phenol is selectively adsorbed onto one wall of a membrane, and the matrix of the membrane is A process as described above, characterized in that the separation is carried out by solubilizing the phenol in the membrane, diffusing the phenol into the membrane and desorbing the phenol from the other wall.
キル置換フェノールを用いる、請求項１記載の方法。2. The method of claim 1, wherein (2) an alkyl-substituted phenol having an alkyl group of 2 to 20 carbon atoms is used.
請求項２記載の方法。(3) the alkyl group has 10 to 18 carbon atoms;
The method according to claim 2.
トが存在する、請求項１記載の方法。(4) The method of claim 1, wherein sodium phenolate or potassium phenolate is present.
ンブランを用いる、請求項１〜４のいずれか一つの項記
載の方法。(5) A method according to any one of claims 1 to 4, characterized in that a dense membrane is selectively permeable to phenol.
る、請求項５記載の方法。(6) The method according to claim 5, wherein an organopolysiloxane is used as the membrane.
る、請求項６記載の方法。(7) The method according to claim 6, wherein polydimethylsiloxane is used as the membrane.
の項記載の方法。(8) The method according to any one of claims 1 to 7, wherein a swelling agent is present.
ａ）の範囲の圧力を用いる、請求項１〜９のいずれか一
つの項記載の方法。(10) 1 to 100 bar (100 to 10,000 kP
10. A method according to any one of claims 1 to 9, using a pressure in the range a).
０℃の範囲の湿度を用いる、請求項１〜１０のいずれか
一つの項記載の方法。(11) 0°C to 120°C, preferably 50°C to 9
11. A method according to any one of claims 1 to 10, using a humidity in the range of 0<0>C.
に用いるのに適したメンブラン。(12) A membrane suitable for use in the method according to any one of claims 1 to 11.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB888827306A GB8827306D0 (en) | 1988-11-23 | 1988-11-23 | Process for separation of phenol |
| GB8827306.5 | 1988-11-23 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02184646A true JPH02184646A (en) | 1990-07-19 |
| JP2819036B2 JP2819036B2 (en) | 1998-10-30 |
Family
ID=10647286
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1300955A Expired - Lifetime JP2819036B2 (en) | 1988-11-23 | 1989-11-21 | How to separate phenol |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US4987273A (en) |
| EP (1) | EP0370555B1 (en) |
| JP (1) | JP2819036B2 (en) |
| KR (1) | KR0149639B1 (en) |
| AU (1) | AU618423B2 (en) |
| CA (1) | CA2003558A1 (en) |
| DE (1) | DE68918055T2 (en) |
| ES (1) | ES2058483T3 (en) |
| GB (1) | GB8827306D0 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5077441A (en) * | 1990-10-05 | 1991-12-31 | The United States Of America As Represented By The Secretary Of Agriculture | Selective gossypol abatement process from oil extraction of cottonseed |
| US5229300A (en) * | 1991-02-19 | 1993-07-20 | The Dow Chemical Company | Membrane method for the determination of an organic acid |
| ES2194777T3 (en) * | 1999-10-19 | 2003-12-01 | Membrane Extraction Tech Ltd | PROCEDURE FOR THE EXTRACTION AND RECOVERY OF PHENOLIC COMPOUNDS OF WATERPROOF FLUIDS. |
| US20040235682A1 (en) * | 2003-05-22 | 2004-11-25 | Chevron Oronite Company Llc | Low emission diesel lubricant with improved corrosion protection |
| CN108211423B (en) * | 2018-02-28 | 2021-01-12 | 北京化工大学 | Method for adsorbing and separating phenolic compounds in oil by using biodegradable compound as adsorbent |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62129105A (en) * | 1985-11-29 | 1987-06-11 | Agency Of Ind Science & Technol | Selective separation process of alcohol |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE466363C (en) * | 1925-09-11 | 1928-10-05 | Schering Kahlbaum Ag | Process for the separation of lipoid mixtures |
| GB1345276A (en) * | 1971-07-27 | 1974-01-30 | Bp Chem Int Ltd | Treatment of effluent from phenol plant |
| US3956112A (en) * | 1973-01-02 | 1976-05-11 | Allied Chemical Corporation | Membrane solvent extraction |
| NL7509076A (en) * | 1974-08-05 | 1976-02-09 | Monsanto Co | PROCEDURE FOR SEPARATING PHENOLS FROM Aqueous MIXTURES. |
| DE2947765C2 (en) * | 1978-11-28 | 1985-09-19 | Koei Chemical Co., Ltd., Osaka | Process for the production of phenols from aqueous solutions |
| US4503267A (en) * | 1983-10-24 | 1985-03-05 | Union Camp Corporation | Extraction of phenolics from hydrocarbons |
-
1988
- 1988-11-23 GB GB888827306A patent/GB8827306D0/en active Pending
-
1989
- 1989-11-08 EP EP89202851A patent/EP0370555B1/en not_active Expired - Lifetime
- 1989-11-08 DE DE68918055T patent/DE68918055T2/en not_active Expired - Fee Related
- 1989-11-08 ES ES89202851T patent/ES2058483T3/en not_active Expired - Lifetime
- 1989-11-20 KR KR1019890016973A patent/KR0149639B1/en not_active Expired - Fee Related
- 1989-11-21 JP JP1300955A patent/JP2819036B2/en not_active Expired - Lifetime
- 1989-11-21 US US07/439,312 patent/US4987273A/en not_active Expired - Fee Related
- 1989-11-21 AU AU45381/89A patent/AU618423B2/en not_active Ceased
- 1989-11-22 CA CA002003558A patent/CA2003558A1/en not_active Abandoned
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62129105A (en) * | 1985-11-29 | 1987-06-11 | Agency Of Ind Science & Technol | Selective separation process of alcohol |
Also Published As
| Publication number | Publication date |
|---|---|
| US4987273A (en) | 1991-01-22 |
| CA2003558A1 (en) | 1990-05-23 |
| KR0149639B1 (en) | 1998-10-15 |
| ES2058483T3 (en) | 1994-11-01 |
| EP0370555A2 (en) | 1990-05-30 |
| AU618423B2 (en) | 1991-12-19 |
| GB8827306D0 (en) | 1988-12-29 |
| EP0370555B1 (en) | 1994-09-07 |
| JP2819036B2 (en) | 1998-10-30 |
| AU4538189A (en) | 1990-05-31 |
| EP0370555A3 (en) | 1991-11-06 |
| KR900007463A (en) | 1990-06-01 |
| DE68918055T2 (en) | 1995-01-26 |
| DE68918055D1 (en) | 1994-10-13 |
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